US4223165A - Process for the hydroxylation of aromatic compounds - Google Patents
Process for the hydroxylation of aromatic compounds Download PDFInfo
- Publication number
- US4223165A US4223165A US05/889,352 US88935278A US4223165A US 4223165 A US4223165 A US 4223165A US 88935278 A US88935278 A US 88935278A US 4223165 A US4223165 A US 4223165A
- Authority
- US
- United States
- Prior art keywords
- hydrogen peroxide
- sub
- reaction
- trifluoromethanesulfonic acid
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 30
- 238000005805 hydroxylation reaction Methods 0.000 title claims description 14
- 230000033444 hydroxylation Effects 0.000 title claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 70
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012429 reaction media Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000011541 reaction mixture Substances 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims 1
- 150000003016 phosphoric acids Chemical class 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 abstract description 7
- 150000008379 phenol ethers Chemical class 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 5
- 230000000640 hydroxylating effect Effects 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- -1 aromatic nitro compounds Chemical class 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 150000001896 cresols Chemical class 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000004967 organic peroxy acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 150000004053 quinones Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- YJBMMHPCGWCCOH-UHFFFAOYSA-N octan-3-yl dihydrogen phosphate Chemical class CCCCCC(CC)OP(O)(O)=O YJBMMHPCGWCCOH-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- SNGARVZXPNQWEY-UHFFFAOYSA-N phenylmethanediol Chemical class OC(O)C1=CC=CC=C1 SNGARVZXPNQWEY-UHFFFAOYSA-N 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
Definitions
- This invention relates to a process for the hydroxylation of aromatic compounds and more particularly to a process for hydroxylating phenols and phenol ethers using hydrogen peroxide.
- U.S. Pat. No. 3,849,502 has proposed a process for the hydroxylation of phenols and their ethers by means of hydrogen peroxide, in the presence of traces of a strong acid and preferably with an agent which complexes the metal ions, such as orthophosphoric acid and polyphosphoric acid.
- Treatment of the phenol in accordance with this patented process gives a mixture of hydroquinone and predominantly of pyrocatechol.
- the present invention provides a process for the hydroxylation of aromatic compounds of the formula: ##STR1## in which R, R 1 and R 2 , are independently selected from the group consisting of hydrogen and alkyl containing from 1 to 3 carbon atoms, and R also represents a hydroxyl or an alkoxy containing from 1 to 3 carbon atoms, which comprises reacting said aromatic compound with hydrogen peroxide, at hydroxylating conditions in a reaction medium comprising trifluoromethanesulfonic acid.
- Another object of this invention is to provide a process for preparing hydroxylated aromatic compounds by effecting the hydroxylation in a medium comprising trifluoromethanesulfonic acid.
- Another object of this invention is to provide an improved process for the hydroxylation of phenol and phenol ethers.
- a further object of this invention is to provide a process for preparing hydroxylated aromatic compounds which does not promote severe corrosion problems.
- a still further object of this invention is to provide a hydroxylation process of phenol which results predominantly in hydroquinone.
- this invention is concerned with a process for introducing hydroxyl substituents on the ring of an aromatic compound, said hydroxylation being effected by treating an aromatic compound with hydrogen peroxide in a reaction medium comprising trifluoromethanesulfonic acid. More particularly, this invention provides a process for hydroxylating an aromatic compound of the formula: ##STR2## in which R, R 1 and R 2 are independently selected from the group consisting of hydrogen and alkyl containing from 1 to 3 carbon atoms, and R also represents a hydroxyl or alkoxy containing from 1 to 3 carbon atoms which comprises reacting said aromatic compound with hydrogen peroxide at hydroxylating conditions in a reaction medium comprising trifluoromethanesulfonic acid.
- R, R 1 and R 2 may represent a methyl, ethyl or any of the isomeric propyl radicals.
- Benzene, toluene, ethylbenzene, cumene, the xylenes, mesitylene, pseudocumene, phenol, the cresols, and alkoxyphenols such as, anisole, phenetole, guaiacol and p-methoxyphenol are suitable starting materials.
- the molar ratio of hydrogen peroxide to the aromatic compound used can vary from 0.025 to 0.3 and preferably between 0.05 and 0.2.
- the degree of conversion of the aromatic compound depends on this ratio. It has been found that the degree of conversion varies directly proportional to the amount of hydrogen peroxide used. However, it is preferable to limit the degree of conversion to 30% and preferably to 15% not to affect the yield of hydroxylic products.
- the initial water content of the reaction mixture must be less than 5%.
- This water can be introduced into the reaction medium by the reactants used. It is advantageous to operate with an aqueous solution which contains at least 50% by weight of hydrogen peroxide in order to introduce less than 5% by weight of water into the reaction medium. It is preferable to introduce the hydrogen peroxide as a solution in trifluoromethanesulfonic acid in order to achieve better control of the reaction and to obtain high reaction outputs.
- the concentration of hydrogen peroxide in solution in the trifluoromethanesulfonic acid expressed as weight of pure hydrogen peroxide relative to the weight of the trifluoromethanesulfonic acid, is generally between 1 and 30% and preferably between 2.5 to 25% of hydrogen peroxide.
- the concentration of the trifluoromethanesulfonic acid used in general is not critical since the trifluoromethane serves as the reaction medium. It has been found that a volume ratio of trifluoromethanesulfonic acid to aromatic compound of at least 0.25 is very suitable. It is appropriate for economic reasons to select volume ratios of trifluoromethanesulfonic acid to aromatic compound not to exceed 20.
- the reaction can be carried out in the presence of another organic solvent such as, chloroform, nitrobenzene or dichloroethane, especially when the temperature chosen is below the melting point of the aromatic compound in order to obtain a more fluid reaction mixture.
- another organic solvent such as, chloroform, nitrobenzene or dichloroethane
- the solution of hydrogen peroxide in trifluoromethanesulfonic acid is added gradually to the reaction mixture consisting of the aromatic compound and the trifluoromethanesulfonic acid which may contain a complexing agent, the mixture being heated beforehand to the reaction temperature.
- the process according to the invention can be carried out at temperatures of between -40° and 10° C. and preferably between -20° and 0° C.
- the chemically active metal ions which are detrimental to the hydroxylation taking place satisfactorily are the ions of transition metals, particularly iron, copper, chromium, cobalt, manganese and vanadium ions.
- the metal ions are derived from the reactants, especially the aromatic compounds, and by the apparatus used.
- the reaction may be carried out in the presence of one or more complexing agents which are stable to hydrogen peroxide, which give complexes which cannot be decomposed by the strong acids present, and in which the metal can no longer exert any chemical activity.
- complexing agents or ligands
- the complexing agent or agents introduced into the reaction medium are selected as a function of the metals present and of their ability to form stable complexes under the reaction conditions.
- the complexing agents which are suitable for a particular case can be determined by means of simple tests.
- Complexing agents such as phoshoric acids (ortho, meta or pyrophosphoric acids or their mixtures) and their alkyl, cycloalkyl or alkaryl acid esters containing up to about 10 carbon atoms in the alkyl portion e.g. ethyl, diethyl, methyl, hexyl, cyclohexyl, benzyl, octyl or ethylhexyl phosphates, and polyphosphoric acids, may be used.
- the amount of complexing agent present in the reaction medium depends on the content of metal ion in this medium. There is no upper limit to the amount of complexing agent that can be used and the amount can be greatly in excess over the amount necessary to complex the metal ions present. In practice, an amount which is from 0.00001 to 5% by weight of the reaction medium is very suitable.
- the reaction mixture is cooled to -21° C. by immersing the beaker into a mixture of acetone and solid carbon dioxide. After cooling, 1.2 cm 3 (2.0347 g) of a solution of hydrogen peroxide in trifluoromethanesulfonic acid, prepared by diluting 0.2527 g of 84.7% strength by weight hydrogen peroxide with 9.9282 g of trifluoromethanesulfonic acid cooled to -20° C., is then gradually charged to the reaction mixture over a two minute period.
- reaction mixture After stirring for 10 minutes at -10° C., the reaction mixture is poured slowly into a 100 cm 3 beaker containing 32 cm 3 of an aqueous solution of potassium acetate (980 g/l). The reaction is exothermic and the reaction mixture is cooled so as to maintain a temperature below 30° C. The neutralized solution is then charged into a liquid-liquid extractor and is extracted with ether under a nitrogen atmosphere continuously for a period of 4 hours.
- the ether solution is distilled to about 50 cm 3 and is then adjusted to 100 cm 3 with ethyl acetate. This solution is analyzed by chromatography on an alumina column.
- the overall yield of diphenols amounts to 74.7% relative to hydrogen peroxide.
- the yield of hydroquinone (HQ) and pyrocatechol (PC) amounts to 51% and 23.7%, respectively, which represents an HQ/PC selectivity of 2.15.
- Example 1 The process of Example 1 is repeated under the conditions and with the results, recorded in TABLE I below:
- Example 1 The process in Example 1 is repeated under the conditions and with the results recorded in TABLE II below.
- the reaction products are analyzed by gas phase chromatography after ether extraction from the reaction mixture.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7523313 | 1975-07-25 | ||
| FR7523313A FR2318851A1 (fr) | 1975-07-25 | 1975-07-25 | Procede d'hydroxylation de composes aromatiques |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05707025 Continuation | 1976-07-20 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/105,776 Division US4301307A (en) | 1975-07-25 | 1979-12-20 | Process for the hydroxylation of aromatic compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4223165A true US4223165A (en) | 1980-09-16 |
Family
ID=9158378
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/889,352 Expired - Lifetime US4223165A (en) | 1975-07-25 | 1978-03-23 | Process for the hydroxylation of aromatic compounds |
| US06/105,776 Expired - Lifetime US4301307A (en) | 1975-07-25 | 1979-12-20 | Process for the hydroxylation of aromatic compounds |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/105,776 Expired - Lifetime US4301307A (en) | 1975-07-25 | 1979-12-20 | Process for the hydroxylation of aromatic compounds |
Country Status (12)
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4301307A (en) * | 1975-07-25 | 1981-11-17 | Rhone-Poulenc Industries | Process for the hydroxylation of aromatic compounds |
| US4453024A (en) * | 1980-06-03 | 1984-06-05 | Pcuk Produits Chimiques Ugine Kuhlmann | Process for the meta-hydroxylation of alkylphenols and the ethers thereof in a superacidic medium |
| US4588845A (en) * | 1983-07-18 | 1986-05-13 | Fmc Corporation | Oxidation of unsaturated organic compounds with hydrogen peroxide |
| US5097078A (en) * | 1989-07-11 | 1992-03-17 | Rhone-Poulenc Chimie | Catalytic hydroxylation of phenols/phenol ethers |
| US5138104A (en) * | 1990-07-26 | 1992-08-11 | Dainippon Ink And Chemicals, Inc. | Process for producing dihydric phenols |
| US5245086A (en) * | 1989-12-05 | 1993-09-14 | Rhone-Poulenc Chimie | Hydroxylation of phenols/phenol ethers |
| US5786519A (en) * | 1996-02-16 | 1998-07-28 | Council Of Scientific & Industrial Research | Process for the preparation of a mixture of guaiacol and p-methoxy phenol |
| US20090192337A1 (en) * | 2008-01-25 | 2009-07-30 | Council Of Scientific & Industrial Research | Process for direct hydroxylation of aromatic hydrocarbons |
| US20100068433A1 (en) * | 2006-09-19 | 2010-03-18 | Valspar Sourcing, Inc. | Food and Beverage Containers and Methods of Coating |
| US20120035397A1 (en) * | 2009-04-06 | 2012-02-09 | Rhodia Operations | Process for the hydroxylation of phenols and of phenol ethers |
| US9133088B1 (en) | 2014-04-30 | 2015-09-15 | Yuan-Zhang Han | Process for hydroxylating phenolic substrate |
| WO2016028490A1 (en) | 2014-08-19 | 2016-02-25 | Yuan-Zhang Han | Process for hydroxylating phenolic substrate |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2942366A1 (de) * | 1979-10-19 | 1981-04-30 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung mehrwertiger phenole |
| FR2548179B1 (fr) * | 1983-06-29 | 1986-06-20 | Ugine Kuhlmann | Procede de preparation d'amino-phenols par hydroxylation d'anilines en milieu superacide au moyen du peroxyde d'hydrogene |
| US4578521A (en) * | 1985-02-04 | 1986-03-25 | Mobil Oil Corporation | Shape-selective catalytic oxidation of phenol |
| FR2744720B1 (fr) * | 1996-02-09 | 1998-04-10 | Rhone Poulenc Chimie | Procede d'hydroxylation de composes phenoliques |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3816545A (en) * | 1971-02-16 | 1974-06-11 | Universal Oil Prod Co | Hydroxylation of aromatic compounds |
| US3849502A (en) * | 1969-12-30 | 1974-11-19 | Rhone Poulenc Sa | Hydroxylation of aromatic compounds |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3407237A (en) * | 1965-11-08 | 1968-10-22 | Universal Oil Prod Co | Preparation of hydroxylated aromatic compounds |
| DE2167040C2 (de) * | 1971-07-17 | 1982-07-08 | Brichima S.p.A., Milano | Verfahren zur Herstellung von Brenzcatechin und Hydrochinon |
| DE2138735A1 (de) * | 1971-08-03 | 1973-03-01 | Haarmann & Reimer Gmbh | Verfahren zur herstellung von polyhydroxybenzolen |
| IT964049B (it) * | 1972-08-18 | 1974-01-21 | Brichima Spa | Processo per la preparazione di difenoli |
| US3839467A (en) * | 1972-08-31 | 1974-10-01 | Universal Oil Prod Co | Preparation of hydroxylated aromatic compounds |
| JPS5217015B2 (enrdf_load_stackoverflow) * | 1973-01-31 | 1977-05-12 | ||
| DE2410742C3 (de) * | 1974-03-06 | 1981-01-08 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von Brenzkatechin und Hydrochinon durch Kernhydroxylierung von Phenol |
| DE2410758C3 (de) * | 1974-03-06 | 1981-01-08 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von mehrwertigen substituierten Phenolen bzw. Monoäthern mehrwertiger Phenole durch Kernhydroxylierung von Phenolen oder Phenoläthern |
| FR2318851A1 (fr) * | 1975-07-25 | 1977-02-18 | Rhone Poulenc Ind | Procede d'hydroxylation de composes aromatiques |
-
1975
- 1975-07-25 FR FR7523313A patent/FR2318851A1/fr active Granted
-
1976
- 1976-07-15 JP JP51083604A patent/JPS6033817B2/ja not_active Expired
- 1976-07-20 CA CA257,370A patent/CA1082742A/fr not_active Expired
- 1976-07-22 BR BR7604773A patent/BR7604773A/pt unknown
- 1976-07-23 NL NL7608218A patent/NL7608218A/xx not_active Application Discontinuation
- 1976-07-23 DE DE2633302A patent/DE2633302C2/de not_active Expired
- 1976-07-23 GB GB30866/76A patent/GB1531604A/en not_active Expired
- 1976-07-23 AT AT543676A patent/AT344141B/de not_active IP Right Cessation
- 1976-07-23 CH CH948276A patent/CH611586A5/xx not_active IP Right Cessation
- 1976-07-23 IT IT25648/76A patent/IT1064854B/it active
- 1976-07-23 BE BE169182A patent/BE844458A/xx not_active IP Right Cessation
-
1978
- 1978-03-23 US US05/889,352 patent/US4223165A/en not_active Expired - Lifetime
-
1979
- 1979-12-20 US US06/105,776 patent/US4301307A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3849502A (en) * | 1969-12-30 | 1974-11-19 | Rhone Poulenc Sa | Hydroxylation of aromatic compounds |
| US3816545A (en) * | 1971-02-16 | 1974-06-11 | Universal Oil Prod Co | Hydroxylation of aromatic compounds |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4301307A (en) * | 1975-07-25 | 1981-11-17 | Rhone-Poulenc Industries | Process for the hydroxylation of aromatic compounds |
| US4453024A (en) * | 1980-06-03 | 1984-06-05 | Pcuk Produits Chimiques Ugine Kuhlmann | Process for the meta-hydroxylation of alkylphenols and the ethers thereof in a superacidic medium |
| US4588845A (en) * | 1983-07-18 | 1986-05-13 | Fmc Corporation | Oxidation of unsaturated organic compounds with hydrogen peroxide |
| US5097078A (en) * | 1989-07-11 | 1992-03-17 | Rhone-Poulenc Chimie | Catalytic hydroxylation of phenols/phenol ethers |
| US5245086A (en) * | 1989-12-05 | 1993-09-14 | Rhone-Poulenc Chimie | Hydroxylation of phenols/phenol ethers |
| US5138104A (en) * | 1990-07-26 | 1992-08-11 | Dainippon Ink And Chemicals, Inc. | Process for producing dihydric phenols |
| US5786519A (en) * | 1996-02-16 | 1998-07-28 | Council Of Scientific & Industrial Research | Process for the preparation of a mixture of guaiacol and p-methoxy phenol |
| US20100068433A1 (en) * | 2006-09-19 | 2010-03-18 | Valspar Sourcing, Inc. | Food and Beverage Containers and Methods of Coating |
| US8927075B2 (en) | 2006-09-19 | 2015-01-06 | Valspar Sourcing, Inc. | Food and beverage containers and methods of coating |
| US9981776B2 (en) | 2006-09-19 | 2018-05-29 | Swimc, Llc | Food and beverage containers and methods of coating |
| US10752400B2 (en) | 2006-09-19 | 2020-08-25 | Valspar Sourcing, Inc. | Food and beverage containers and methods of coating |
| US20090192337A1 (en) * | 2008-01-25 | 2009-07-30 | Council Of Scientific & Industrial Research | Process for direct hydroxylation of aromatic hydrocarbons |
| US7781622B2 (en) | 2008-01-25 | 2010-08-24 | Council Of Scientific & Industrial Research | Process for direct hydroxylation of aromatic hydrocarbons |
| US20120035397A1 (en) * | 2009-04-06 | 2012-02-09 | Rhodia Operations | Process for the hydroxylation of phenols and of phenol ethers |
| US8791308B2 (en) * | 2009-04-06 | 2014-07-29 | Rhodia Operations | Process for the hydroxylation of phenols and of phenol ethers |
| US9133088B1 (en) | 2014-04-30 | 2015-09-15 | Yuan-Zhang Han | Process for hydroxylating phenolic substrate |
| WO2016028490A1 (en) | 2014-08-19 | 2016-02-25 | Yuan-Zhang Han | Process for hydroxylating phenolic substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2318851B1 (enrdf_load_stackoverflow) | 1977-12-09 |
| ATA543676A (de) | 1977-11-15 |
| JPS5214733A (en) | 1977-02-03 |
| BE844458A (fr) | 1977-01-24 |
| DE2633302A1 (de) | 1977-02-17 |
| FR2318851A1 (fr) | 1977-02-18 |
| CH611586A5 (enrdf_load_stackoverflow) | 1979-06-15 |
| GB1531604A (en) | 1978-11-08 |
| IT1064854B (it) | 1985-02-25 |
| CA1082742A (fr) | 1980-07-29 |
| US4301307A (en) | 1981-11-17 |
| DE2633302C2 (de) | 1985-07-11 |
| AT344141B (de) | 1978-07-10 |
| BR7604773A (pt) | 1977-08-02 |
| JPS6033817B2 (ja) | 1985-08-05 |
| NL7608218A (nl) | 1977-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4223165A (en) | Process for the hydroxylation of aromatic compounds | |
| US3849502A (en) | Hydroxylation of aromatic compounds | |
| US2727926A (en) | Catalytic oxidation of armoatic carboxylic acids to phenols | |
| US4208536A (en) | Hydroxylation of aromatic compounds | |
| US5434317A (en) | Hydroxylation of phenolic compounds | |
| US5331103A (en) | Process for monohydroxylation of phenolic compounds | |
| US3928477A (en) | Production of phenols from decomposition of aromatic hydroperoxides | |
| US4238417A (en) | Decomposition of cumene hydroperoxide and recovery of boron trifluoride catalyst | |
| US4267379A (en) | Decomposition of cumene hydroperoxide and recovery of boron trifluoride catalyst | |
| EP0107427A1 (en) | Process for oxidizing a phenol to a p-benzoquinone | |
| US4182917A (en) | Process for the preparation of polyhydric phenols | |
| EP2417092B1 (fr) | Procede d'hydroxylation de phenols et d'ethers de phenols | |
| PL86971B1 (enrdf_load_stackoverflow) | ||
| CA1101436A (en) | Process for the preparation of polyhydric phenols | |
| EP0432006B1 (fr) | Procédé d'hydroxylation de phénols et d'éthers de phénols | |
| KR20110015690A (ko) | 페놀의 히드록실화 방법 | |
| US4387252A (en) | Process for the preparation of polyhydric phenols | |
| US4453024A (en) | Process for the meta-hydroxylation of alkylphenols and the ethers thereof in a superacidic medium | |
| US5710292A (en) | Process for the selective oxidation of aromatic compounds | |
| US5075463A (en) | Preparation of quinones | |
| JP6700252B2 (ja) | フェノール基材をヒドロキシル化するための方法及びヒドロキシル化されたフェノール基材の製造方法 | |
| US3699175A (en) | Hydroxylation of aromatics | |
| EP0408418B1 (fr) | Procédé d'hydroxylation de phénols et d'éthers de phénols | |
| EP0749408B1 (en) | Improved process for the production of beta-diketone | |
| PL85551B1 (enrdf_load_stackoverflow) |